Halomethyl ether esters



-nuclear halomethyl substituted arom having the general formula Patented July 28, 1942 UNITED STATES PATEN T 'OFF'ICE HALOMETHYL ETHER ESTERS Herman A. Bruson and Clinton W.

Philadelphia, Pa., Company, Phllade Delaware No Drawing.

Serial No.

7 Claims. "(C

a carbon atom of the ring. Itrelates further to a process for preparing these ethers. More particularly it relates to the preparation of atic ethers (halCH:)n-R-X-A--Y 10 wherein hal is a member of the group conslsting or chlorineand bromine, n is an integer less than three, R is a carbocyclic aromatic radical, X is a member of the group consisting '01 O and S, A is an all-xylene group, the chain of which may be interrupted by a member or the group consisting of 0 and S, and Y is amember oi the group consisting of OH, --O.alkyl,

' O-aryl, OCO-alkyl, -OCOaryl, CO-

alkyl, -COaryl, -COOalkyl, COOH, and

These halomethyl compounds may be prepared by condensing an ether of the general'iormula RX A-Y with formaldehyde and hydrogen chloride or hydrogen bromide. The reaction takes place readily in concentrated hydrochloric or hydrobror'nic acid solution at temperatures of about 10-60 C. without splitting the etherlinkages. The compounds thus obtained may be used inthe preparation of wetting agents, resins, insecticides, mothproofing agents, tanning materials, and other industrial products.

Typical ethers which are suitable for the preparation of these new halomethyl compounds are the following:

Application Octob MacMullen,

assignors to & Haas lphia, Pa.,'a corporation 0! er 15', 1941 415,035 a and compounds containing I the radical- R-O-A- in which A- ls a polyalkylene ether group, such as in which R'is an aromatic residue, which may contain other nuclear substituentssuch as alkyl; aralkyl, cycloalkyl, aryl, nitro, halogen, acyl groups. etc. but must be tree of radicals or groups which are destroyed by the hydrogen halide or the formaldehyde. Such groups are, for example, the amino, diazo, and aldehyde groups. It must also be free of hydroxyl groups which would cause condensation of the formaldehyde in a different manner. These aromatic radicals must have at least one replaceable nu.- clear' hydrogen atom and, in case more than one is available, more than one (halCHz) group ,canbe introduced into-the aromatic radical. The aromatic radical may be mononuclear or polynuclear such as a benzene, naphthalene, phenanthrene, anthracene, or other polynuclear radical. Y

. The reaction is carried out in general by suspending the and ether in the aqueous hydrohalogen acid containing the formaldehyde and passing in dry hydrogen halide at temperatures of about 10 to C. The aryl ether may also be dissolved in a suitable non-reactive organic solvent such as petroleum ether, ethylene dichloride, etc. The formaldehyde may be used in the form of an aqueous solution or as paraformaidehyde. The products obtained are usually low-melting solids or' thick oils.

reagents shownas it may be otherwise practiced within the scope of the appended claims.

Example 1 A stream of dry hydrogen chloride was passed into a mixture of 100 grams of phenoxyethoxyethyl chloride, 102 grams of 37% formaldehyde, and 300 cc. of concentrated hydrochloric acid for 8 hours-at a temperature of about 30 C., the

reaction mass being stirred throughout this period. A light brown oil formed which was separated, dissolved in benzene and washed with ice water. anhydrous sodium sulfate, filtered, and the sol-' vent evaporated in vacuo, leaving 116 grams of oil which'on cooling changed to a white solid. This material was purified by distillation in vacuo. It boiled at 210- 215 C./ mm. and the distillate solidified to a crystalline mass which on recrystallization from petroleum ether was The benzene solution was dried with phenyl p-chloroethoxyethyl sulfide having the formula:

cl-cmcanls-bzmo-clmm Example 5 A mixture of 118 grams or o-chlorophenoxyethoxyethyl chloride, 90 grams of 37% formaldehyde, and 300 cc. of concentrated hydrochloric acid was heated at 50-60" C. and stirred vigorously while a stream of dry hydrogen chloride was passed through the mixture for 18 hours. a

A brown oil separated which was washed and dried as described above. On evaporation of the solvent a clear, light brown oil weighing 126 grams remained. This was chloromethyl '0- obtained in the form of white crystals having a melting point of 52-54 C. The determination of chlorine content showed it'to be di(chloromethyl) phenoxyethoxyethyl chloride hav-in the probable formula:

cicm-Qo-omcmo omcmcl cmcl ' Example 2 A mixture of 156 grams of phenoxyethyl chloride, 500 grams of formaldehyde, and 500 cc. of concentrated hydrochloric acid was heated v at -55 C. and stirred vigorously while a stream of dry hydrogen chloride was passed in for 8 hours. The semi-solid material was purified by washing with cold methyl alcohol. The white crystalline solid obtained, having a melting point of 60-62 C. was di(chloromethyl) phenoxyethyl chloride having the probable formula:

mom-Qo-cmcmcr Emample 3 A' mixture of 122 grams of phenoxyethoxyethoxyethyl chloride, 102 grams of 37% formaldehyde, and 300 cc. of concentrated hydrochloric acid was stirred vigorously and a stream of dry hydrogen chloride was passed into the mixture for 3 hours at SO-33 C. A light brown oil separated which was dissolved in benzene, washed with ice water the solution dried with anhydrous sodium sulfate,.filtered, and the benzene evaporated in vacuo. The residue was a clear, light brown oil weighing 136 grams. A chlorine determination showed this to be di(chloromethyl) phenoxyethoxyethoxyethyl chloride having the formula:

' chlorophenoxyethoxyethyl chloride having the probable formula:

ClCH-QO CIHAO CIHACI Example .6

A mixture of 131 grams of o-sec-octyl phenoxyethoxyethoxyethyl chloride, grams of 37%, formaldehyde, and 300 cc. of concentrated hydrochloric acid was heated at 50-60 C. while a stream of dry hydrogen chloride passed in for about 20 hours. The product was'isolated as described above. The light brown oil was o-secoctyl chloromethyl phenoxyethoxyethoxyethyl ch l oride having the formula:

cmwmnon-mm-ocmlomnio Came! in moi In a similar manner dodecyl phenoxyethoxyethyl chloride was converted to its chloromethyl derivative which is a pale yellow oil.

Example 7. I

A mixture of 160 grams of p-phenyl phenoxyethonethoxyethyl chloride, 142 grams, 01 37% formaldehyde, and 300 cc. of concentrated hydro chloric acid was heated at 50-60 C. and stirred while a stream of dry hydogen chloride was passed in for 10 hours. 151 grams of a dark.

brown oil was isolated in the usual manner. This product --was chloromethyl p-phenyl phenoxyethoxyethoxyethyl chloride.

Example; 81.6 grams of p-cyclohexyl phenoxyethoxyethoxyethyl chloride 41 grams of 37% formalde- Example 4 A mixture of 44 of p-cloroethoxyethyl Dhenyl sulfide, C1CaH40-C2H4SC5Hs, grams of 37% formaldehyde, and 200 cc. of concenhyde, and 200 cc. of concentrated hydrochloric acid were heated at 50-60 C. and a stream of dry hydrogen chloride passed in for 11 hours; A clear, dark brown oil weighing 68 grams was isolated as described above. The product obtained was p-cyclohexyl chloromethyl phenoxyethoxyethoxyethyl chloride having the probable formula:

CECE: CH:

CH lHloCIHAOGiHlC/l CHICQ:

Example 9 83.6 grams ofp-benzyl phenoxyethoxyethoxyethyl chloride, 81 grams of 37% formaldehyde,

and 200 cc. of concentrated hydrochloric acid were heated at 40-50 C'. and a stream of dry hydrogen chloride passed in for 8 hours. The clear, brown oil, separated as described above, was chloromethyl p-benzyl phenoxyethoxyethoxyethyl chloride.

Example methyl phenoxyethoxyethox'yethyl chloride hav ing the probable formula:

QuHrF-CeHKCHa)0C:H4-OCzHr-O-CrHlCl Example 11 A mixture of 156 grams of p-ter-octyl phenoxyethoxyethyl chloride, grams of paraformaldehyde, and 150 grams of ethylene dichloride was stirred while a stream of dry hydrogen chloride was passed in for 17 hours at about 30 C. A red oil layer separated which was washed with cold water, dried with anhydrous sodium sul- 'fate, fllter,ed, and the ethylene dichloride distilled off in vacuo. A clear, brown oil weighing 137 grams was obtained. The product was pter-octyl-chloromethyl phenoxyethoxyethyl chloride having the probable formula:

Example 12 A mixture of 178.4 grams of p-ter-octyl phenoxyethoxyethoxyethyl chloride, 41 grams of 37% 1 formaldehyde, 300 cc. of concentrated hydrochloric acid, and 12 grams of powdered anhydrous zinc chloride was stirred and cooled at about 0 C. while a stream of dry hydrogen chloride passed through the mixture for about 6 hours. This mixture was poured onto ice and d0 the product extracted with benzene. The benzene solution'was washed with ice waterydried, filtered, and the solventremoved in vacuo. The clear pale yellow oil remaining was chloromethyl p-ter-octyl phenoxyethoxyethoxyethyl chloride.

' Example 13 A mixture of 32 grams of o-phenyl phenoxyethanol, grams of 30% formaldehyde, and 90 cc. of concentrated hydrochloric acid was heated 60 at 35-50 C. anda stream of dry hydrogen chloride passed in for 7 hours. The product was isolated in the usual manner. It was an oil which on analysis was found to be di(chloromethyl) -o-phenyl phenoxyethanol.

Example 14 A mixture of 76 grains of phenoxy aceticacid, 90 grams of 37% formaldehyde, and 300 cc. of

while a stream of dry hydrogen chloride'was passed in for 7 hours at 30-40? C. A resinous mass was obtained which was washed and dried on a porous plate. Analysis indicated it to be the dichloromethyl derivative of phenoxy ethyl acetate.

Example 16 A mixture of 46 grams of o-nitro phenoxyethoxyethyl chloride, 41 grams of 37% formaldehyde, and 200 cc. of concentrated hydrochloric acid was stirred while a stream of dry hydrogen chloride passed in at 30-60 C. for about 8 hours. A brown oil separated which was purifled in the usual manner. The product obtained was chloromethyl o-nitro phenoxyethoxyethyl chloride having the probable formula:

cwH cmro-cnn-o-mmm N01 I Example 17 A mixture of grams 'of p-cyclohexyl phenoxythoxyethyl n-butyl ether, 51 grams of 37% I formaldehyde, and 200 cc. of concentrated hydrochloric acid was stirred while a streani of dry hydrogen chloride was passed in at 30-50 C. for 7 hours. A clear, yellow oil was obtained which was chloromethyl p-cyclohexyl phenoxy- "ethoxyethyl n-butyl ether having. ,the probable formula: i I

CeHnCe MCHaCDOCahLOCaHsOCJia I I Example 18 "A mixture of 156 grams of p-ter-octyl phenoxyethoxy'ethyl chloride, 30 grams of paraform.-" aldehyde, and 150 grams of petroleum ether (B. P. 30-60" c.) was stirred while a stream or dry hydrogen chloride was passed in for 16 hours at 30-60 C. The turbid brown solution was washed with cold water, dried with anhydrous sodium sulfate, filtered, and the solvent distilled off in vacuo. A brown oil remained which was chloromethyl p-ter-octyl phenoxyethoxyethyl chloride.

1 Example 1 9 A mixture of 26 grams of phenoxyethoxyethoxyethyl sulfide, 41 grams of 37% formaldehyde, and 200 cc. of concentrated hydrochloric acid'was vigorously stirred while a stream ofdry hydrogen chloride was passed in for about 8 hours without heating or cooling. A very viscous layer separated which was washed and dried on a porous plate. The brown elastic mass was tetra(chloromethyl) phenoxyethoxyethoxyethyl concentrated hydrochloric acid was heated at 60 sulfide having the probable formula:

0103' oc|mocrmoc,H. s -c,momemento-Q0150! moi moi 50-60 C. and a stream of dry hydrogen chloride. I

passed in for 6% hours. A viscous mass separated which was washed and dried on a porous Example 13 i A mixture of grams of phenoxyethyl acetate, 90 grams of 37% formaldehyde, and 300 Example 20 tate, 90 grams of 37% formaldehyde, and 300' '70 cc. of concentrated hydrochloric acid was stirred I while a stream of dry hydrogen chloride was passed in for 7 hours without heating or cooling.- A yellow layer formed which was dissolved in benzene, washed, dried, and the benzene removed cc. of concentratedhydrochloric acid was stirred 7:5 in vacuo. A clear yellow oil remained which was butyl dichlommethyl pherroxy' acetate having the probable formula:

" cram-Qocmcoocun Example Z1 was chloromethyl diisobutyl phenoxyethoxyethoxyethyl benzoate.

This application is a continuation-in-part of application Serial No. 228,145, filed September 2, 1938, now United States Patent No, 2,266,737,

.issued December 23, 1941, in which there are A mixture of 87.5 grams of phenoiwethoxyv ethyl dodecyl ether, 61 gramsof 37% formaldehyde, and 200 cc. of concentrated hydrochloric .acid was stirred while a stream of dry hydrogen chloride was passed in without heating or cooling for 11 hours. The oil layer which separated was purified as described above. The product was a clear amber oil which was di-(chloromethyl) -phenox yethoxyethyl dodecyl ether having the probable formula:

CICHQO crmo cane cane The bromo-methyl and di(bromo-methyl) derivatives of compounds of the above type may be obtained by replacing the hydrogen chloride with hydrogen bromide. In some cases the aryl' polyalkylene ether halides giveresinous products which are diflicult to isolate. o-Methoxy phenoxyethoxyethyl chloride gives a viscous con-' centrate analyzing for the dichloromethyl derivative. p-Naphthoxy-ethoxyehhyi chloride when treated with formaldelrvdeand hydrochloric acid yields a resinous chloromethyl derivative.

Example 22 Example 23 A mixture of 180 grams of phenoxy ethyl acetate CcHsOCzHrOCOCHa, 244 grams of 37% aqueous formaldehyde, and 200 grams of concentrated hydrochloric acid was stirred and saturated with gaseous hydrogen chloride at 35-50 C. for 8 hours, Th oil layer was separated, taken up in benzen, washed with ice water, and the solvent removed in vacuo. The deep yellow, viscous oil was chlorometh yl phenoxy ethyl acetate containing some of the dichloromethyl phenoxy ethyl acetate.

Example 24 A mixture of 221 grams of diisobutyl phenoxyethoxyethoxyethyl benzoate CaHrvCsHaOCaHcbCzHiOCzHaOCOCoHs 122 grams of 37% aqueous formaldehyde, and

200 grams of concentrated hydrochloric acid was stirred and saturated with gaseous hydrogen chloride for 8 hours at 3045 C. The reaction mixture was diluted with ice water, the oil taken up in benzene and washed, dried, and the solvent removed in vacuo. The dark brown oil obtained claimed those compounds of the formula in which Y is chlorine or bromine. There are claimed herein those compounds in which Y in the above formula represents 0CO--alkyl, OCO-aryl, or CO0alky1. The alkyl group may be a short or long chain, a branched or straight chain, such as methyl, ethyl, propyl, isopropyl, butyl, heptyl, octyl, isooctyl, dodecyl, cetyl, octadecyl, etc. As an aryl group there may be used any of the aromatic nuclei which have been described above as suitable for R, including aryl groups having halomethyl substituents. We claim: 1. Compounds of the formula:

(hall-CH2) n-n-x-a-sz wherein hal is a member .of the group consisting of chlorine and bromine n is an integer less than three, R is a carbocyclic aromatic radical, X is a member of th class consisting of oxygen and sulfur, A is an alkyiene group, the chain of which may be interrupted by a member of the class consisting of oxygen and sulfur, and Y is a member of the class consisting of OCOalky1,

2. Compounds of the formula;

(CICHR) n-R:0AY

wherein n is an integer less than three,Ri a. car- -b0cy1ic aromatic radical, A is an alkylene group,

and Y is selected from a member of the class consisting of OCOalkyl, OCOaryl, and -C0.0a1kyl.

3. Compounds of the formula:

wherein n is an integer less than three, R is a phenyl group, A is a polyalkyiene ether chain, and Y is selected from a member of the class consisting of --0CO-alkyl, --0COaryl, and CQOa1ky1.

4. Compounds of the formula:

wherein n is an integer less than three, R is a phenyl nucleus, and A is an alkylene group,

5. Compounds of the formula:

- wherein n is an integer less than three, R is a phenyl nucleus, and A is a polyalkylene ether group.

6. Compounds of the formula:

(ClCHa) n -R(OCH2CH2) y0COalkyl wherein 1L is an integer less than three, 11 is an integer from one to ten inclusive, and R i a phenyl nucleus.

7. As a new compound,

(ClCHa) 2C H3OC2H4OCOCH3 HERMAN A. BRUSON; CLINTON W. MACMUILEN. 

